JP2000226593A - Lubricating oil additive and lubricating oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an additive for lubricating oil as an ashless detergent and dispersant having excellent high-temperature stability (high-temperature detergency) and dispersing fine particles, and lubrication containing the additive for lubricating oil. An oil composition is provided. SOLUTION: (a) at least one compound selected from specific substituted hydroxyaromatic carboxylic acid ester derivatives and (b) selected from the group consisting of boron-containing alkylamide, boron-containing alkenylamide and boron-containing hydroxybenzylamine To provide a lubricating oil additive comprising at least one type of boron-containing ashless dispersant, and a lubricating oil composition comprising the lubricating oil base oil and the lubricating oil additive. Things.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an additive for lubricating oil and a lubricating oil composition, and more particularly, to an additive for lubricating oil having excellent high-temperature stability (high-temperature detergency), and strict exhaust gas regulations in the future. The present invention relates to a lubricating oil composition suitable for a lubricating oil for an internal combustion engine, etc., corresponding to the above.

[0002]

2. Description of the Related Art Conventional ashless dispersants include succinimide-based and hydroxybenzylamine-based dispersants.
It is widely used as an additive for gasoline, diesel engine oil and the like because of its remarkable fine particle dispersing action. And, they also have a synergistic effect with zinc dialkyldithiophosphate and metal type detergents, and are one of extremely important additives for lubricating oil. However, in recent years, it has been often pointed out that stability at high temperatures (high-temperature cleanliness) is not sufficient.

Conventional lubricating oils for internal combustion engines are usually base oils and ashless dispersants such as polybutenyl succinimide, metal-type detergents such as alkaline earth metal sulfonates and phenates, and zinc alkyldithiophosphates. However, there is a problem that the metal component in the additive component is generated as an oxide or a sulfate by combustion and is involved in environmental pollution and the like.

[0004] In recent years, out of the internal combustion engine, environmental pollution measures have become an important issue by the exhaust gas regulations, such as particulates and NO _X in particular diesel engine.
Particulate traps and N
There is an exhaust gas purifying device, such as O _X removal catalyst but, in a conventional internal combustion engine lubricating oils, because of the clogging problem due to the metal oxides and sulfides produced by combustion, such as the metal oxides and sulfides There is a need for a lubricating oil for internal combustion engines that can minimize emissions.

[0005] As one solution to the future measures against exhaust gas, a methanol engine has attracted attention. In diesel engines, light oil is sprayed into the engine by an injection pump, but lubrication in the pump is self-lubricated by the light oil itself. On the other hand, in a methanol engine, since the lubricity of methanol itself is low, it is usual to inject engine oil into an injection pump. In that case,
Due to poor compatibility between methanol and engine oil, additives precipitate in methanol, and especially in the case of metal-type detergents, there is a problem that metal components such as calcium may clog the nozzle injection port. There is a demand for a lubricating oil for an internal combustion engine that minimizes the oil content.

[0006] As a measure against such future exhaust gas, for example, (3,5-di-t-butyl-)
An ashless lubricating oil composition containing a 4-hydroxyphenyl) carboxylic acid alkyl ester, a succinimide-based ashless dispersant and an ashless antioxidant has been proposed (JP-A-4-353598). ). However, this composition has a problem that high-temperature stability (high-temperature detergency) cannot be sufficiently satisfied.

On the other hand, US Pat. No. 4,098,708 proposes esters of alkyl-substituted hydroxyaromatic carboxylic acids having at least about 10 carbon atoms and derivatives thereof as dispersants for lubricating oils and fuel oils. As a suitable alcohol component of the ester, a monohydric or polyhydric hydrocarbon alcohol is mentioned, and specific examples thereof include substituted phenols such as cresol. However, in the case of this ester as well, the high-temperature stability is not similarly satisfactory.

Accordingly, the present inventors have previously found that a specific substituted hydroxyaromatic carboxylic acid ester derivative is excellent in high-temperature stability (high-temperature detergency) (Japanese Patent Application Laid-open No.
JP-A-62371, JP-A-7-165671,
Japanese Unexamined Patent Publication No. Hei 7-267904) and further research.

[0009]

DISCLOSURE OF THE INVENTION The present invention overcomes the drawbacks of the prior art, has excellent high-temperature stability (high-temperature detergency), and is used as an ashless cleaning and dispersing agent having a fine particle dispersing action. It is an object of the present invention to provide a lubricating oil additive and a lubricating oil composition containing the lubricating oil additive.

[0010]

Means for Solving the Problems As a result of further intensive studies, the present inventors have found that a mixture of a specific substituted hydroxy aromatic carboxylic acid ester derivative and a specific boron-containing ashless dispersant is used for lubricating oil. It has been found that the object of the present invention can be effectively achieved by using it as an additive, and the present invention has been completed. That is, the present invention relates to (a) the following general formula (I)

[0011]

Embedded image

[Wherein, R ¹ and R ² each represent an organic group having 6 or more carbon atoms, which may be the same or different, and a, b, c, d and e each represent 1
≤ a ≤ 3, 1 ≤ b ≤ 3, 0 ≤ c ≤ 3, 1 ≤ d ≤ 3, 1 ≤
e ≦ 3, 3 ≦ (a + b + e) ≦ 6 and 1 ≦ (c + d) ≦
An integer satisfying the relationship of 5 is shown. Further, when R ¹ and R ² are a plurality, the plurality of R ¹ and R ² may be the same or different in each. ] Or the following general formula (I
I)

[0013]

Embedded image

[Wherein R^Three, R^FourAnd R^FiveRespectively
Represents an organic group having 6 or more carbon atoms, each of which is the same
May also be different, f, g, h, i, j, k and m
Are 0 ≦ f ≦ 3, 0 ≦ g ≦ 3, 1 ≦ (f + g)
≦ 3,0 ≦ h ≦ 4,0 ≦ i ≦ 3,1 ≦ (h + i) ≦ 6
0 ≦ j ≦ 3, 1 ≦ k ≦ 3, 1 ≦ m ≦ 3, 3 ≦ (f + g +
h + i + m) ≦ 8 and 1 ≦ (j + k) ≦ 5
Indicates an integer. Also, R ^Three, R^FourAnd R^FiveWhere there are multiple
If multiple R^Three, R^FourAnd R^FiveIs in each
They may be the same or different. Represented by the substituted hydro
Selected from xyloxycarboxylic acid ester derivatives
At least one compound and (b) a boron-containing alkyl
Amides, boron-containing alkenylamides and boron-containing amides
At least one selected from the group consisting of droxybenzylamine
Lubrication containing a kind of boron-containing ashless dispersant
In addition to providing oil additives, lubricating base oils
Providing a lubricating oil composition containing an effective amount of lubricant additives
Is what you do.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The additive for lubricating oil of the present invention comprises (a) at least one compound selected from the substituted hydroxyaromatic carboxylic acid ester derivatives represented by the general formula (I) or (II) and (b) boron-containing compound. It contains at least one boron-containing ashless dispersant selected from the group consisting of alkylamides, boron-containing alkenylamides, and boron-containing hydroxybenzylamines.

The components (a) and (b) will be described in detail in order. (A ) Component At least one compound selected from the substituted hydroxy aromatic carboxylic acid ester derivatives represented by the general formula (I) or (II). The general formulas (I) and (II)
In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represent an organic group having 6 or more carbon atoms. As the organic group having 6 or more carbon atoms, a hydrocarbon group having preferably 6 to 100 carbon atoms, more preferably 8 to 20 carbon atoms can be exemplified. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aralkyl group and the like, which have a non-hydrocarbon substituent and a hetero atom in the chain or ring. Is also good. Specifically, hydrocarbon groups such as hexyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, triacontyl group, and groups derived from olefin polymers such as polyethylene, polypropylene, polybutene, etc. Can be mentioned. When a low-viscosity substituted hydroxyaromatic carboxylic acid ester derivative is desired, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be a substantially linear hydrocarbon group. preferable. The R ¹ and R
² may be the same or different, and R ³ , R ⁴ and R ⁵ may be the same or different.

In the general formula (I), a, b, c,
d and e are respectively 1 ≦ a ≦ 3, 1 ≦ b ≦ 3, 0 ≦ c
≦ 3,1 ≦ d ≦ 3,1 ≦ e ≦ 3,3 ≦ (a + b + e) ≦
An integer satisfying the relationship of 6 and 1 ≦ (c + d) ≦ 5 is shown.
When b is 2 or 3, a plurality of R ¹ may be the same or different, and when d is 2 or 3, a plurality of R ² may be the same or different.

Further, in the general formula (II), f,
g, h, i, j, k and m are respectively 0 ≦ f ≦ 3,0
≦ g ≦ 3,1 ≦ (f + g) ≦ 3,0 ≦ h ≦ 4,0 ≦ i ≦
3,1 ≦ (h + i) ≦ 6,0 ≦ j ≦ 3,1 ≦ k ≦ 3,1
≦ m ≦ 3, 3 ≦ (f + g + h + i + m) ≦ 8 and 1 ≦
An integer satisfying the relationship (j + k) ≦ 5 is shown. h is a few
Or in the case of 4, a plurality of R ³ may be the same or different, and when i is 2 or 3, the plurality of R ⁴ may be the same or different. When k is 2 or 3, a plurality of R ⁵ may be the same or different.

Specific examples of the substituted hydroxyaromatic carboxylic acid ester derivative represented by the general formula (I) include:
(Hexylhydroxybenzoic acid) hexylphenyl ester, (hexylhydroxybenzoic acid) dodecylphenyl ester, (octylhydroxybenzoic acid) octylphenyl ester, (nonylhydroxybenzoic acid) nonylphenylester, (nonylhydroxybenzoic acid) hexadecylphenylester , (Dodecylhydroxybenzoic acid) nonylphenyl ester, (dodecylhydroxybenzoic acid) dodecylphenylester, (dodecylhydroxybenzoic acid) hexadecylphenylester,
(Hexadecylhydroxybenzoic acid) hexylphenyl ester, (hexadecylhydroxybenzoic acid) dodecylphenylester, (hexadecylhydroxybenzoic acid) hexadecylphenylester, (eicosylhydroxybenzoic acid) eicosylphenylester, (C 11 Mixed alkyl hydroxybenzoic acid having from 15 to 15) mixed alkyl phenyl ester having 11 to 15 carbon atoms, (long chain alkyl [for example, a group derived from polydecene having 30 or more carbon atoms, derived from polybutene having a weight average molecular weight of 400 or more] Group] hydroxybenzoic acid) dodecylphenyl ester, (long-chain alkyl [eg, a group derived from polydecene having 30 or more carbon atoms, weight-average molecular weight of 400]
Above-mentioned groups derived from polybutene] hydroxybenzoic acid) long-chain alkyl [eg, groups derived from polydecene having 30 or more carbon atoms, groups derived from polybutene having a weight-average molecular weight of 400 or more] phenyl ester, (hexylhydroxyl (Benzoic acid) hexyl hydroxyphenyl ester, (octyl hydroxybenzoic acid) octyl hydroxyphenyl ester, (dodecyl hydroxybenzoic acid) nonyl hydroxyphenyl ester, (dodecyl hydroxybenzoic acid) dodecyl hydroxyphenyl ester, (hexadecyl hydroxybenzoic acid) dodecyl hydroxy Phenyl ester, (hexadecylhydroxybenzoic acid) hexadecylhydroxyphenyl ester,
(Eicosyl hydroxybenzoic acid) eicosyl hydroxyphenyl ester, (mixed alkyl hydroxybenzoic acid having 11 to 15 carbon atoms) mixed alkyl hydroxyphenyl ester having 11 to 15 carbon atoms, (long chain alkyl [for example, having 30 or more carbon atoms] Group derived from polydecene, group derived from polybutene having a weight average molecular weight of 400 or more] hydroxybenzoic acid) dodecyl hydroxyphenyl ester, (long chain alkyl [eg, group derived from polydecene having 30 or more carbon atoms, weight average A group derived from a polybutene having a molecular weight of 400 or more] hydroxybenzoic acid) a long-chain alkyl [eg, a group derived from a polydecene having a carbon number of 30 or more, a group derived from a polybutene having a weight average molecular weight of 400 or more] hydroxyphenyl ester, (Hexyl dihydro (Benzoic acid) hexylphenyl ester, (nonyldihydroxybenzoic acid) nonylphenyl ester, (nonyldihydroxybenzoic acid) dodecylphenylester, (dodecyldihydroxybenzoic acid) nonylphenylester, (dodecyldihydroxybenzoic acid) dodecylphenylester, (hex (Decyl dihydroxy benzoic acid) hexadecyl phenyl ester, (eicosyl dihydroxy benzoic acid) hexadecyl phenyl ester, (eicosyl dihydroxy benzoic acid) eicosyl phenyl ester, (C 11-11
Mixed alkyl dihydroxybenzoic acid) having 11 to 1 carbon atoms
5, a mixed alkyl phenyl ester, (long chain alkyl [eg, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] dihydroxybenzoic acid) dodecyl phenyl ester, (long chain Alkyl [eg, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] dihydroxybenzoic acid)
Long-chain alkyl [eg, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] phenyl ester, (hexyldihydroxybenzoic acid) hexylhydroxyphenyl ester, (nonyldihydroxybenzoic acid ) Nonylhydroxyphenyl ester, (nonyldihydroxybenzoic acid)
Dodecyl hydroxyphenyl ester, (dodecyl dihydroxybenzoic acid) nonyl hydroxyphenyl ester, (dodecyl dihydroxybenzoic acid) dodecyl hydroxyphenyl ester, (hexadecyl dihydroxybenzoic acid) hexadecyl hydroxyphenyl ester,
(Eicosyl dihydroxybenzoic acid) hexadecyl hydroxyphenyl ester, (eicosyl dihydroxybenzoic acid) eicosyl hydroxyphenyl ester, (mixed alkyl dihydroxybenzoic acid having 11 to 15 carbon atoms)
Mixed alkylhydroxyphenyl ester having 11 to 15 carbon atoms, (long-chain alkyl [eg, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] dihydroxybenzoic acid) dodecylhydroxy Phenyl ester, (long-chain alkyl [eg, a group derived from polydecene having 30 or more carbon atoms, group derived from polybutene having a weight-average molecular weight of 400 or more] dihydroxybenzoic acid) long-chain alkyl [eg, having 30 or more carbon atoms Groups derived from polydecene,
Hydroxyphenyl ester derived from polybutene having a weight average molecular weight of 400 or more].

On the other hand, specific examples of the substituted hydroxy aromatic carboxylic acid ester derivative represented by the general formula (II) include (hexylhydroxynaphthoic acid) hexylphenyl ester, (hexylhydroxynaphthoic acid) hexadecylphenyl ester, (Nonylhydroxynaphthoic acid) nonylphenyl ester, (dodecylhydroxynaphthoic acid) dodecylphenylester, (hexadecylhydroxynaphthoic acid) hexadecylphenylester, (dodecylhydroxynaphthoic acid) eicosylphenylester, (eicosylhydroxynaphthoic acid) Eicosylphenyl ester, (mixed alkylhydroxynaphthoic acid having 11 to 15 carbon atoms) mixed alkylphenylester having 11 to 15 carbon atoms, (long-chain alkyl [for example, having 30 or more carbon atoms] Group derived from polydecene, group derived from polybutene having a weight average molecular weight of 400 or more] hydroxynaphthoic acid) dodecylphenyl ester, (long chain alkyl [eg, group derived from polydecene having 30 or more carbon atoms, weight average molecular weight] A group derived from polybutene of 400 or more] hydroxynaphthoic acid) a long-chain alkyl [eg, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] phenyl ester, (hexyl) (Hydroxynaphthoic acid) dodecyl hydroxyphenyl ester, (octyl hydroxynaphthoic acid) dodecyl hydroxyphenyl ester, (dodecyl hydroxynaphthoic acid) dodecyl hydroxyphenyl ester, (dodecyl hydroxynaphthoic acid) hexadecylhydro Xyphenyl ester, (hexadecylhydroxynaphthoic acid) hexadecylhydroxyphenylester, (hexadecylhydroxynaphthoic acid) eicosylhydroxyphenylester, (mixed alkylhydroxynaphthoic acid having 11 to 15 carbon atoms) mixed with 11 to 15 carbon atoms Alkyl hydroxyphenyl ester, (long-chain alkyl [eg, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight-average molecular weight of 400 or more] hydroxynaphthoic acid) dodecyl hydroxyphenyl ester, (long-chain alkyl [For example, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] hydroxynaphthoic acid) long-chain alkyl [for example, a group derived from polydecene having 30 or more carbon atoms] Group derived from polybutene having a weight average molecular weight of 400 or more] hydroxyphenyl ester, (hexyldihydroxynaphthoic acid) hexylphenyl ester, (hexyldihydroxynaphthoic acid) hexadecylphenyl ester, (nonyldihydroxynaphthoic acid) nonylphenyl ester , (Dodecyldihydroxynaphthoic acid) dodecylphenyl ester, (dodecyldihydroxynaphthoic acid) eicosylphenyl ester,
(Hexadecyldihydroxynaphthoic acid) hexadecylphenyl ester, (eicosyldihydroxynaphthoic acid) eicosylphenyl ester, (C 11-11
Mixed alkyl dihydroxynaphthoic acid) having 11 to 11 carbon atoms
15 mixed alkyl phenyl esters, (long chain alkyl [eg, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] dihydroxynaphthoic acid) dodecyl phenyl ester, (long chain Alkyl [for example, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] dihydroxynaphthoic acid) long-chain alkyl [for example, a group derived from polydecene having 30 or more carbon atoms] , A group derived from polybutene having a weight average molecular weight of 400 or more] phenyl ester, (hexyldihydroxynaphthoic acid) dodecylhydroxyphenylester, (octyldihydroxynaphthoic acid) dodecylhydroxyphenylester, (dodecyldihydroxynaphthoic acid) Decyl-hydroxyphenyl ester, (dodecyl dihydroxy naphthoic acid) hexadecyl-hydroxyphenyl ester, (hexadecyl dihydroxy-naphthoic acid) hexadecyl-hydroxyphenyl ester, (hexadecyl-dihydroxy-naphthoic acid) eicosyl hydroxyphenyl ester, (carbon number 11 to 15
Mixed alkyl dihydroxynaphthoic acid) having 11 to 11 carbon atoms
15 mixed alkyl hydroxyphenyl esters, (long-chain alkyl [eg, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] dihydroxynaphthoic acid) dodecyl hydroxyphenyl ester, ( Long-chain alkyl [for example, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight-average molecular weight of 400 or more] dihydroxynaphthoic acid) long-chain alkyl [for example,
A group derived from polydecene having 30 or more carbon atoms, and a group derived from polybutene having a weight average molecular weight of 400 or more] hydroxyphenyl ester.
Among these substituted hydroxy aromatic carboxylic acid ester derivatives, the following general formula (III)

[0021]

Embedded image

(Wherein R ¹ , R ² , b, d and e are the same as above, and the sum of b and e is 2 to 5) or the following general formula (III ′)

[0023]

Embedded image

Where R ³ , R ⁴ , R ⁵ , h, k and m
Is the same as described above, and n represents 0, 1 or 2, the sum of h and n is 1 to 6, and the sum of h, m and n is 2 to 7. The compound represented by the formula (1) is preferable. In the lubricating oil additive of the present invention, the component (a) may be composed of one kind of the compound represented by the general formula (I), or may be composed of two or more kinds. In addition, the compound represented by the general formula (II) may be composed of one kind or two or more kinds. Further, one or more compounds represented by the general formula (I) and the compound represented by the general formula (I
It may be composed of one or more compounds represented by I).

( B) Component At least one boron-containing ashless dispersant selected from the group consisting of boron-containing alkylamides, boron-containing alkenylamides, and boron-containing hydroxybenzylamines. Preferred examples of the boron-containing alkylamide and the boron-containing alkenylamide include those obtained by reacting or mixing a reaction product of an alkyl or alkenylcarboxylic acid with an amine compound having at least two -NH- groups with a boron-containing compound. Can be.

The above-mentioned alkyl or alkenyl carboxylic acids have 6 to 40 carbon atoms, preferably 14 to 20 carbon atoms.
And specifically include myristic acid, isomyristic acid, palmitic acid, isopalmitic acid, stearic acid, isostearic acid, arachiic acid, isoarachinic acid, myristoleic acid, and the like.
Zomalic acid, oleic acid and the like can be mentioned. Specific examples of the amine compound include polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. As the boron-containing compound, specifically, boric acid, metaboric acid,
Tetraboric acid, boric anhydride, boric acid esters and the like can be mentioned.

Next, as the boron-containing hydroxybenzylamine, preferred are those obtained by reacting or mixing hydroxybenzylamine with a boron-containing compound. The above-mentioned hydroxybenzylamine is obtained by subjecting an alkylphenol and an amine compound to a Mannich reaction with an aldehyde.

Specific examples of the alkylphenols include phenols having an alkyl group having 9 to 150 carbon atoms. Specific examples of the amine compound include polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. Examples of the above aldehydes include formaldehyde and acetaldehyde. Examples of the boron-containing compound include the same compounds as described above. The boron content in the boron-containing ashless dispersant (b) is preferably 0.05 to 5% by weight.
And more preferably 0.1 to 3% by weight.

In the lubricating oil additive of the present invention, (b)
The component may be composed of one kind of the above-mentioned boron-containing alkylamide or boron-containing alkenylamide, or may be composed of two or more kinds. The boron-containing hydroxybenzylamine may be composed of one kind, or may be composed of two or more kinds. Furthermore, it may be composed of one or more of the boron-containing alkylamide or boron-containing alkenylamide and one or more of the boron-containing hydroxybenzylamine.

In the lubricating oil additive of the present invention, at least one kind selected from the substituted hydroxy aromatic carboxylic acid ester derivatives represented by the general formula (I) or (II), which is the component (a), And the boron-containing ashless dispersant as the component (b) are mixed in a weight ratio of 1:99 to 99: 1, preferably 10:90 to 90:
Preferably, it is in the range of 10.

Next, the lubricating oil composition of the present invention is obtained by blending an effective amount of the above lubricating oil additive with a lubricating base oil. The effective amount is 0.1 to 3 based on the total amount of the lubricating oil.
0% by weight, preferably 1 to 20% by weight. As the lubricating base oil, mineral oil or synthetic oil or a combination thereof is used. The mineral oil may be any fraction such as a paraffinic mineral oil, a naphthenic mineral oil, or an aromatic mineral oil, and may be any that has been subjected to any purification method such as solvent refining, hydrorefining, or hydrocracking. As the synthetic oil, polyphenyl ether, polyvinyl ether and hydrogenated products thereof, alkylbenzene, alkylnaphthalene, ester-based, polyglycol-based or polyolefin-based synthetic oil, and the like can be used. The kinematic viscosity as lubricating oil fraction (100 ° C.) is usually 1 to 50 mm ² / s, preferably from 3 to 10 mm ² / s.

Examples of ester synthetic oils include esters of alcohols with monobasic acids or dibasic acids and the like, for example, dibasic acids having 6 to 16 carbon atoms and linear or branched alcohols having 5 to 20 carbon atoms. A synthetic oil consisting of an ester obtained by the reaction can be used. In particular, adipic acid ester, sebacic acid ester, azelaic acid ester, trimethylolpropane ester, trimethylolethane ester, pentaerythritol ester, neopentyl glycol ester and the like are preferable. Polyolefin synthetic oils include ethylene, propylene, butylene,
Liquid products obtained by the low polymerization or copolymerization of lower olefins such as octene, decene and dodecene, mixtures thereof and hydrogenated products thereof are suitable. Also, complex esters composed of dibasic acids, glycols and monobasic acids, and α-
Olefin / dibasic acid copolymer esters can also be used.

In the lubricating oil composition of the present invention, as the base oil, one kind of the above mineral oils may be used, two or more kinds may be used in combination, and one kind of the above synthetic oils may be used. Two or more kinds may be used in combination. Further, one or more mineral oils and one or more synthetic oils may be used in combination.

The lubricating oil composition of the present invention may contain, in addition to the aforementioned additive composition for a lubricant, various lubricating oil compositions conventionally used in lubricating oil compositions, if desired, as long as the object of the present invention is not impaired. Appropriate amounts of additional components such as antioxidants, rust inhibitors, defoamers, viscosity index improvers, pour point depressants, antiwear agents, demulsifiers, metal detergents and the like can be added.

The lubricating oil composition of the present invention can be used, for example, as a lubricating oil for an internal combustion engine, gear oil, bearing oil, transmission oil, shock absorber oil, industrial lubricating oil, etc. It is useful as a lubricating oil composition for engines and methanol engines.

[0036]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. Reference Example 1 A commercially available fatty acid amide (a reaction product of isostearic acid and tetraethylenepentamine) 5 was placed in a 200-ml separable flask equipped with a nitrogen inlet tube.
After adding 0 g and 10 g of boric acid, the mixture was heated and stirred at 130 ° C. for 6 hours while bubbling with nitrogen. The reaction mixture was filtered by heating to obtain a boron-containing fatty acid amide. The boron content of the obtained boron-containing fatty acid amide was 2.8% by weight.

REFERENCE EXAMPLE 2 In the same manner as in Reference Example 1, a commercially available hydroxybenzylamine (Mannich reaction product of a phenol having an alkyl group having a distribution of 50 to 100 carbon atoms and tetraethylenepentamine) was used instead of the commercially available fatty acid amide. ) Was obtained in the same manner as in Example 1 except that (1) was used. The boron content of the obtained boron-containing hydroxybenzylamine is 2.2% by weight.
Met.

Example 1 In a mineral oil of a 500 neutral fraction, 2.5 parts of (dodecylsalicylic acid) dodecylphenyl ester (formula (IV)) based on the total amount of the lubricating oil composition
By weight, 7.5% by weight of the boron-containing fatty acid amide obtained in Reference 1 was blended to prepare a lubricating oil composition. The performance of this lubricating oil composition was evaluated by the following hot tube test. Table 1 shows the results.

[0039]

Embedded image

(Hot tube test conditions) 0.3 ml / hr of test oil in a glass tube having an inner diameter of 2 mm, air 1
The flow of 0 ml / min was continued for 16 hours while maintaining the temperature of the glass tube at 310 ° C. The lacquer adhering to the glass tube was compared with the color sample, and a score was given as 10 points for transparent and 0 points for black, and the weight of the lacquer adhering to the glass tube was measured. The higher the score and the lower the lacquer weight, the higher the performance.

Example 2 A lubricating oil composition was prepared in the same manner as in Example 1, except that the boron-containing hydroxybenzylamine obtained in Reference Example 2 was used instead of the boron-containing fatty acid amide. The performance of this lubricating oil composition was evaluated by the hot tube test described above. Table 1 shows the results.

Example 3 In a mineral oil of a 500 neutral fraction, (dodecylsalicylic acid) dodecylphenyl ester (formula (IV)) was added in an amount of 1.0 based on the total amount of the lubricating oil composition.
1.0% by weight of the boron-containing fatty acid amide obtained in Reference Example 1, 4.0% by weight of other ashless detergent and dispersant, 5.0% by weight of metal detergent and dispersant, and 2. 0% by weight
And 0.3% by weight of a rust preventive were blended to prepare a lubricating oil composition. The performance of this lubricating oil composition was evaluated by the hot tube test described above. Table 1 shows the results.

Example 4 A lubricating oil composition was prepared in the same manner as in Example 3, except that the boron-containing hydroxybenzylamine obtained in Reference Example 2 was used instead of the boron-containing fatty acid amide. The performance of this lubricating oil composition was evaluated by the hot tube test described above. Table 1 shows the results.

Comparative Example 1 A lubricating oil composition was prepared in the same manner as in Example 1, except that a commercially available fatty acid amide (same as Reference Example 1) was used instead of the boron-containing fatty acid amide. The performance of this lubricating oil composition was evaluated by the hot tube test described above. Table 1 shows the results.

Comparative Example 2 A lubricating oil composition was prepared in the same manner as in Example 1, except that a commercially available hydroxybenzylamine (same as Reference Example 2) was used instead of the boron-containing fatty acid amide. The performance of this lubricating oil composition was evaluated by the hot tube test described above. Table 1 shows the results.

Comparative Example 3 A lubricating oil composition was prepared in the same manner as in Example 3 except that (dodecylsalicylic acid) dodecylphenyl ester and boron-containing fatty acid amide were not blended. The performance of this lubricating oil composition was evaluated by the hot tube test described above. Table 1 shows the results.

As can be seen from Table 1, the lubricating oil compositions of Examples 1 to 4 using the lubricating oil additive comprising the substituted hydroxy aromatic carboxylic acid ester derivative of the present invention and a boron-containing ashless dispersant The product showed good results in the hot tube test and showed excellent high-temperature stability (high-temperature detergency).

[0048]

[Table 1]

[0049]

The additive for lubricating oil comprising the specific substituted hydroxyaromatic carboxylic acid ester derivative of the present invention and the specific boron-containing ashless dispersant of the present invention has high-temperature stability (high-temperature detergency). It is excellent, has fine particle dispersibility, and is useful as an excellent ashless detergent and dispersant for lubricating oils. Therefore, the lubricating oil composition of the present invention can be made ashless,
In particular, it is useful as a diesel engine oil and a methanol engine oil compliant with future emission regulations.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C10N 30:08 40:25

Claims (4)

[Claims] (A) The following general formula (I):[Wherein, R¹And R^TwoIs an organic having 6 or more carbon atoms
Denote groups, which may be the same or different
A, b, c, d and e are respectively 1 ≦ a ≦ 3,1
≤ b ≤ 3, 0 ≤ c ≤ 3, 1 ≤ d ≤ 3, 1 ≤ e ≤ 3, 3 ≤
(A + b + e) ≦ 6 and 1 ≦ (c + d) ≦ 5
Indicates an integer to be added. Also, R¹And R^TwoIf there are multiple
Is a multiple R¹And R^TwoIs the same in each
It may be different. Or the following general formula (II):[Wherein, R^Three, R^FourAnd R^FiveEach have 6 or more carbon atoms
Organic groups, which are the same or different
F, g, h, i, j, k and m are
0 ≦ f ≦ 3,0 ≦ g ≦ 3,1 ≦ (f + g) ≦ 3,0 ≦ h
≦ 4, 0 ≦ i ≦ 3, 1 ≦ (h + i) ≦ 6, 0 ≦ j ≦ 3
1 ≦ k ≦ 3, 1 ≦ m ≦ 3, 3 ≦ (f + g + h + i + m)
Indicates an integer satisfying the relationship of ≦ 8 and 1 ≦ (j + k) ≦ 5
You. Also, R ^Three, R^FourAnd R^FiveIf there are multiple
R^Three, R^FourAnd R^FiveAre the same or different in each
It may be. A substituted hydroxy aromatic represented by the formula:
At least one selected from carboxylic acid ester derivatives
A compound and (b) a boron-containing alkylamide,
U-containing alkenyl amides and boron-containing hydroxy
At least one member selected from the group consisting of
Additive for lubricating oils containing boron-containing ashless dispersant
Agent. 2. The additive for lubricating oil according to claim 1, wherein the boron content in the boron-containing ashless dispersant (b) is 0.05 to 5% by weight. 3. A lubricating oil composition comprising an effective amount of the lubricating oil additive according to claim 1 mixed with a lubricating base oil. 4. The lubricating oil composition according to claim 3, wherein the lubricating oil is a lubricating oil for an internal combustion engine.